US4885368A - Radical ion salts - Google Patents
Radical ion salts Download PDFInfo
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- US4885368A US4885368A US07/125,823 US12582387A US4885368A US 4885368 A US4885368 A US 4885368A US 12582387 A US12582387 A US 12582387A US 4885368 A US4885368 A US 4885368A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/611—Charge transfer complexes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to novel radical ion salts based on N,N-dicyanoquinonediimines.
- the present invention relates to novel radical ion salts of biscyanimines of the formula ##STR3## where R 1 , R 2 , R 3 and R 4 independently of one another are each hydrogen, methyl, ethyl, phenyl, methoxy, ethoxy, fluorine, chlorine or bromine and R 1 or R 1 and R 3 may furthermore be tert-butyl or R 1 and R 2 and/or R 3 and R 4 together may in each case form a radical of the formula ##STR4## where z is 0, 1, 2 or 3 and the fused, aromatic rings are unsubstituted or monosubstituted or disubstituted by chlorine, bromine, methyl and/or methoxy, M m ⁇ is an m-valent alkali metal, alkaline earth metal, transition metal, tin, lead, thallium, ammonium, phosphonium, arsonium or stibonium ion, k is from 1 to 5, l is from 0.1 to 4,
- the novel salts (I) (complexes) have a high electrical conductivity, which as a rule is clearly or substantially higher in single crystals.
- the conductivities of the salts (I) are substantially superior to those of the known radical ion salts based on tetracyanoquinodimethane and copper or silver.
- the prior art TCNQ.Cu salt has a conductivity of 0.005 S.cm -1 [L. R. Melby et al., J. Amer. Chem. Soc. 84 (1962), 3374], while the corresponding radical ion salt according to the invention (Example 37) has a conductivity of 0.02 S.cm -1 .
- a number of the compounds (I) are thermally stable at about 300° C. or above. Accordingly, the novel complexes are useful, for example, as electrical semiconductors and photoconductors, for the antistatic treatment of plastics, as electrode and storage material in electric batteries, for the production of solar cells, in fuel cells, for the conversion of radiation and for the production of electronic components. Microcrystalline films of the novel radical ion salts can be used for the production of bistable electrical switching elements.
- R 1 , R 2 , R 3 and R 4 are as follows:
- R 1 , R 2 , R 3 and R 4 are identical and are each hydrogen, fluorine, chlorine, methyl or methoxy or
- R 1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R 2 , R 3 and R 4 are each hydrogen, or
- R 1 and R 4 are identical and are each chlorine, methyl or methoxy and R 2 and R 3 are each hydrogen, or
- R 1 and R 2 are identical and are each chlorine, methyl, methoxy or phenyl and R 3 and R 4 are each hydrogen, or
- R 1 and R 3 are identical and are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R 2 and R 4 are each hydrogen or
- R 1 , R 2 and R 3 are each methyl and R 4 is hydrogen, or
- R 1 is methyl, R 3 is chlorine or bromine and R 2 and R 4 are each hydrogen, or
- R 1 and R 2 together form a radical of the formula ##STR5## where z is 0, 1, 2 or 3 and the fused aromatic ring is unsubstituted or monosubstituted or disubstituted by chlorine, methyl and/or methoxy, and R 3 and R 4 independently of one another are each hydrogen, chlorine or methyl or
- R 1 and R 2 , and R 3 and R 4 in each case together form a radical of the formula ##STR6## where z is 0, 1, 2 or 3 and the fused aromatic rings are unsubstituted or monosubstituted or disubstituted by chlorine, methyl and/or methoxy.
- Suitable ions M m ⁇ are ions of metals whose redox potential is less than or equal to that of silver, eg. ammonium, phosphonium, arsonium and stibonium.
- metal ions are those of the alkali metals, such as lithium, sodium, potassium, rubidium and cesium, those of the alkaline earth metals, such as calcium, strontium and barium, those of the transition metals, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium and mercury, and those of tin, lead and thallium.
- alkali metals such as lithium, sodium, potassium, rubidium and cesium
- alkaline earth metals such as calcium, strontium and barium
- transition metals such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium and mercury, and those of tin, lead and thallium.
- ammonium M m ⁇ examples are tetra-C 1 -C 4 -alkylammonium, tetraphenyl-C 1 -C 3 -alkylammonium, phenyl-C 1 -C 3 -alkyl-tris-C 1 -C 4 -alkylammonium, C 1 -C 4 -alkylpyridinium, N-phenyl-C 1 -C 3 -alkylpyridinium, quinolinium, N-C 1 -C 4 -alkylquinolinium, N-phenyl-C 1 -C 3 -alkylquinolinium and the corresponding isoquinolinium compounds, phenazinium, N-C 1 -C 4 -alkylphenazinium and N-phenyl-C 1 -C 3 -alkylphenazinium.
- Particularly suitable phosphonium, arsonium and stibonium ions are those which are derived from the triphenyl compounds.
- M m ⁇ are Li.sup. ⁇ , Na.sup. ⁇ , K.sup. ⁇ , Rb.sup. ⁇ , Cs.sup. ⁇ , Mg 2 ⁇ , Ca 2 ⁇ , Ba 2 ⁇ , Sr 2 ⁇ , Cr 3 ⁇ , Mn 2 ⁇ , Fe 2 ⁇ , Fe 3 ⁇ , Co 2 ⁇ , Ni 2 ⁇ , Cu.sup. ⁇ , Cu 2 ⁇ , Zn 2 ⁇ , Ag.sup. ⁇ , Cd 2 ⁇ , Sn 2 ⁇ , Pb 2 ⁇ , Pb 4 ⁇ , Tl.sup. ⁇ , Tl 3 ⁇ , triphenylmethylphosphonium, triphenylmethylarsonium, triphenylmethylstibonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrabenzylammonium, tetra(2-phenylethyl
- Preferred M m ⁇ ions are copper(I) and silver(I) ions, tetramethylammonium, tetraethylammonium, tetrabenzylammonium, trimethylbenzylammonium, triethylbenzylammonium, quinolinium, pyridinium, N-methylpyridinium, N-ethylquinolinium, N-methylquinolinium, phenazinium and N-methylphenazinium, of which copper (I), silver(I), pyridinium, N-methylpyridinium, quinolinium, N-methylquinolinium, phenazinium and N-methylphenazinium are particularly preferred.
- the radical ion salts (I) according to the invention can be prepared by various processes.
- One route is the reaction of N,N'-dicyanoquinonediimines of the formula (II) ##STR7## where R 1 , R 2 , R 3 and R 4 have the above meanings, with halides, preferably iodides, of the above cations M m ⁇ in a molar ratio of from 1:0.5 to 1:3, in a solvent, if necessary at elevated temperatures.
- Suitable solvents are dichloromethane, chloroform, tetrahydrofuran, 1,1,1-trichloroethane, acetonitrile, benzene, toluene, chlorobenzene and dichlorobenzene.
- the radical ion salts are isolated in a conventional manner by filtration under suction.
- novel radical ion salts (I) may furthermore be prepared by reacting an N,N'-dicyanoquinonediimine of the formula (II) with a metal M, preferably in powdered form, in a molar ratio of from 1:1 to 1:0.2, in one of the abovementioned solvents which is inert to the metal, if necessary at elevated temperatures.
- the radical ion salts are isolated in a conventional manner by filtration under suction.
- the novel radical ion salts (I) may furthermore be prepared by electrolysis of a solution which contains an N,N'-dicyanoquinonediimine of the formula (II) and a salt containing one of the above cations (M m ⁇ ) in one of the above solvents, at from room temperature to -30° C.
- the temperature depends on the solubility of the N,N'-dicyanoquinoneimine.
- electrolysis is carried out at ⁇ 0° C., in particular from -10° to -30° C., in order as far as possible to avoid any decomposition which may occur.
- the radical ion salts are isolated in a conventional manner by filtration under suction.
- the yield of the radical ion salt (I) depends on the duration of electrolysis and on the solubility of (I) in the solvent used for the electrolysis, since isolation of the dissolved salt (I) from the electrolysis solution containing the conductive salt is very difficult.
- the radical ion salts (I) according to the invention can also be prepared by reacting the lithium salt of an N,N'-dicyanoquinonediimine of the formula (II) with a salt containing one of the above cations (M m ⁇ ) in a solvent such as methanol, ethanol, propanol, water, acetonitrile or a mixture of these.
- Microcrystalline films which consist of the novel radical ion salts can be produced in a conventional manner by immersing a metallic body in a solution of an N,N'-dicyanoquinoneimine in one of the above solvents, preferably at elevated temperatures.
- N,N'-dicyanoquinonediimine (II) A solution of copper(I) iodide in acetonitrile is added to a solution of N,N'-dicyanoquinonediimine (II) in acetonitrile. During this procedure, a dark precipitate separates out and is filtered off under suction and washed with acetonitrile.
- the N,N'-dicyanoquinonediimines (II) used are characterized by the substituents in columns 2 to 5 of Table 1.
- Example 2 The procedure described in Example 1 is followed, except that a solution of copper(I) bromide in tetrahydrofuran is used, and a solution of 2-chloro-5-methyl-N,N'-dicyano-1,4-benzoquinonediimine is added dropwise to this.
- the corresponding radical ion salt of the formula ##STR9## is obtained in a yield of 93%. Mp.>350° C.
- N,N'-Dicyanoquinonediimines (II) are stirred with silver powder in acetonitrile at room temperature. Insoluble material is filtered off under suction.
- the N,N'-dicyanoquinonediimines (II) used are characterized by R 1 to R 4 in columns 2 to 5 of Table 2.
- the salts (Ib) are characterized by the decomposition point, elemental analysis and the electrical conductivity.
- Electrolysis is carried out in a cell which holds 60 ml of liquid and is divided into 3 compartments by two G4 glass frits. Each compartment can be filled or emptied under protective gas, independently of one another.
- the electrodes are present in the outer compartments. Dividing the cell into three parts prevents byproducts formed at the anode from penetrating into the cathode space.
- Electrodes Two platinum sheets measuring 20 ⁇ 10 ⁇ 1 mm are used as the electrodes.
- the electrodes and the cell are cleaned with a mixture of 35% strength hydrogen peroxide and concentrated sulfuric acid each time before being used. They are then washed with water, after which the cell is steeped in distilled water for 1 day in order to remove final traces of acid. The cell is then dried at 120° C.
- electrolysis By adjusting the cell temperature in a heatable bath, electrolysis can be effected at defined temperatures.
- Electrolysis of the solution is not taken to completion, in order to avoid excessive reduction.
- the N,N'-dicyanoquinonediimines (II) characterized in Table 3 by R 1 , R 2 , R 3 and R 4 are subjected to electrolysis together with salts containing cations M m ⁇ , in acetonitrile, using procedures similar to those described in Examples 15 and 16. Electrolysis is carried out at between room temperature (25° C.) and -20° to -25° C., depending on the solubility of the N,N'-dicyanoquinonediimines (II) used. The yield of (I) is dependent on the duration of electrolysis and on the solubility of the resulting compound (I) in acetonitrile. Isolation of the dissolved compound (I) from the acetonitrile solution formed during electrolysis and containing the conductive salt is very difficult.
- the salts (Ic) obtained are characterized in columns 9 to 12 by their decomposition points and elemental analysis, and in some cases by their conductivities.
Abstract
Novel radical ion salts of the formula ##STR1## wherein R1, R2, R3 and R4 independently of one another are each hydrogen, methyl, ethyl, phenyl, methoxy, ethoxy, fluorine, chlorine or bromine, or R1 or R1 and R3 may furthermore be tert-butyl and/or R1 and R2 and/or R3 and R4 together may in each case form a radical of the formula ##STR2## where z is 0, 1, 2 or 3, and the fused aromatic rings are unsubstituted or monosubstituted or disubstituted by chlorine, bromine, methyl and/or methoxy, Mm⊕ is an m-valent alkali metal, alkaline earth metal, transition metal, tin, lead, thallium, ammonium, phosphonium, arsonium or stibonium ion, k is from 1 to 5, l is from 0.1 to 4, m is from 1 to 3, n is from 0.1 to 4, x is from 0 to 2 and y is from 0 to 6, and k, l, n, x and y may furthermore be non-integral numbers and (l+x)=n.m, are electrically conductive in the crystalline state. A number of the salts are stable at 300° C. and above.
The salts (I) are useful as electrical semiconductors and photoconductors, as electrode or storage material, in electric batteries, etc.
Description
This application is a continuation of application Ser. No. 876,399, filed on June 20, 1986, now abandoned.
The present invention relates to novel radical ion salts based on N,N-dicyanoquinonediimines.
Radical ion salts of tetracyanoquinodimethanes and copper or silver are known [Appl. Phys. Lett. 34 (1979), 405, J. Amer. Chem. Soc. 102 (1980), 3659 and Chem. Skripta 17 (1981), 219].
The present invention relates to novel radical ion salts of biscyanimines of the formula ##STR3## where R1, R2, R3 and R4 independently of one another are each hydrogen, methyl, ethyl, phenyl, methoxy, ethoxy, fluorine, chlorine or bromine and R1 or R1 and R3 may furthermore be tert-butyl or R1 and R2 and/or R3 and R4 together may in each case form a radical of the formula ##STR4## where z is 0, 1, 2 or 3 and the fused, aromatic rings are unsubstituted or monosubstituted or disubstituted by chlorine, bromine, methyl and/or methoxy, Mm⊕ is an m-valent alkali metal, alkaline earth metal, transition metal, tin, lead, thallium, ammonium, phosphonium, arsonium or stibonium ion, k is from 1 to 5, l is from 0.1 to 4, m is from 1 to 3, n is from 0.1 to 4, x is from 0 to 2 and y is from 0 to 6, and k, l, n, x and y may furthermore be non-integral numbers and (l+x)=n.m.
In the microcrystalline state, the novel salts (I) (complexes) have a high electrical conductivity, which as a rule is clearly or substantially higher in single crystals. For example, the conductivities of the salts (I) are substantially superior to those of the known radical ion salts based on tetracyanoquinodimethane and copper or silver. Thus, the prior art TCNQ.Cu salt has a conductivity of 0.005 S.cm-1 [L. R. Melby et al., J. Amer. Chem. Soc. 84 (1962), 3374], while the corresponding radical ion salt according to the invention (Example 37) has a conductivity of 0.02 S.cm-1. A number of the compounds (I) are thermally stable at about 300° C. or above. Accordingly, the novel complexes are useful, for example, as electrical semiconductors and photoconductors, for the antistatic treatment of plastics, as electrode and storage material in electric batteries, for the production of solar cells, in fuel cells, for the conversion of radiation and for the production of electronic components. Microcrystalline films of the novel radical ion salts can be used for the production of bistable electrical switching elements.
Specific examples for combinations of R1, R2, R3 and R4 are as follows:
(a) R1, R2, R3 and R4 are identical and are each hydrogen, fluorine, chlorine, methyl or methoxy or
(b) R1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R2, R3 and R4 are each hydrogen, or
(c) R1 and R4 are identical and are each chlorine, methyl or methoxy and R2 and R3 are each hydrogen, or
(d) R1 and R2 are identical and are each chlorine, methyl, methoxy or phenyl and R3 and R4 are each hydrogen, or
(e) R1 and R3 are identical and are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R2 and R4 are each hydrogen or
(f) R1, R2 and R3 are each methyl and R4 is hydrogen, or
(g) R1 is methyl, R3 is chlorine or bromine and R2 and R4 are each hydrogen, or
(h) R1 and R2 together form a radical of the formula ##STR5## where z is 0, 1, 2 or 3 and the fused aromatic ring is unsubstituted or monosubstituted or disubstituted by chlorine, methyl and/or methoxy, and R3 and R4 independently of one another are each hydrogen, chlorine or methyl or
(i) R1 and R2, and R3 and R4, in each case together form a radical of the formula ##STR6## where z is 0, 1, 2 or 3 and the fused aromatic rings are unsubstituted or monosubstituted or disubstituted by chlorine, methyl and/or methoxy.
Suitable ions Mm⊕ are ions of metals whose redox potential is less than or equal to that of silver, eg. ammonium, phosphonium, arsonium and stibonium.
Examples of metal ions are those of the alkali metals, such as lithium, sodium, potassium, rubidium and cesium, those of the alkaline earth metals, such as calcium, strontium and barium, those of the transition metals, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium and mercury, and those of tin, lead and thallium.
Examples of ammonium Mm⊕ are tetra-C1 -C4 -alkylammonium, tetraphenyl-C1 -C3 -alkylammonium, phenyl-C1 -C3 -alkyl-tris-C1 -C4 -alkylammonium, C1 -C4 -alkylpyridinium, N-phenyl-C1 -C3 -alkylpyridinium, quinolinium, N-C1 -C4 -alkylquinolinium, N-phenyl-C1 -C3 -alkylquinolinium and the corresponding isoquinolinium compounds, phenazinium, N-C1 -C4 -alkylphenazinium and N-phenyl-C1 -C3 -alkylphenazinium.
Particularly suitable phosphonium, arsonium and stibonium ions are those which are derived from the triphenyl compounds.
Specific examples of Mm⊕ are Li.sup.⊕, Na.sup.⊕, K.sup.⊕, Rb.sup.⊕, Cs.sup.⊕, Mg2⊕, Ca2⊕, Ba2⊕, Sr2⊕, Cr3⊕, Mn2⊕, Fe2⊕, Fe3⊕, Co2⊕, Ni2⊕, Cu.sup.⊕, Cu2⊕, Zn2⊕, Ag.sup.⊕, Cd2⊕, Sn2⊕, Pb2⊕, Pb4⊕, Tl.sup.⊕, Tl3⊕, triphenylmethylphosphonium, triphenylmethylarsonium, triphenylmethylstibonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrabenzylammonium, tetra(2-phenylethyl)ammonium, trimethylbenzylammonium, triethylbenzylammonium, pyridinium, N-methyl- and N-ethylpyridinium, N-methyl-2-methylpyridinium, N-methyl-3-methylpyridinium, N-methyl-4-methylpyridinium, N-benzylpyridinium, quinolinium, N-methyl, N-ethyl- and N-benzylquinolinium, phenazinium and N-methyl-, N-ethyl- and N-benzylphenazinium.
Preferred Mm⊕ ions are copper(I) and silver(I) ions, tetramethylammonium, tetraethylammonium, tetrabenzylammonium, trimethylbenzylammonium, triethylbenzylammonium, quinolinium, pyridinium, N-methylpyridinium, N-ethylquinolinium, N-methylquinolinium, phenazinium and N-methylphenazinium, of which copper (I), silver(I), pyridinium, N-methylpyridinium, quinolinium, N-methylquinolinium, phenazinium and N-methylphenazinium are particularly preferred.
The radical ion salts (I) according to the invention can be prepared by various processes. One route is the reaction of N,N'-dicyanoquinonediimines of the formula (II) ##STR7## where R1, R2, R3 and R4 have the above meanings, with halides, preferably iodides, of the above cations Mm⊕ in a molar ratio of from 1:0.5 to 1:3, in a solvent, if necessary at elevated temperatures. Examples of suitable solvents are dichloromethane, chloroform, tetrahydrofuran, 1,1,1-trichloroethane, acetonitrile, benzene, toluene, chlorobenzene and dichlorobenzene. The radical ion salts are isolated in a conventional manner by filtration under suction.
The novel radical ion salts (I) may furthermore be prepared by reacting an N,N'-dicyanoquinonediimine of the formula (II) with a metal M, preferably in powdered form, in a molar ratio of from 1:1 to 1:0.2, in one of the abovementioned solvents which is inert to the metal, if necessary at elevated temperatures. The radical ion salts are isolated in a conventional manner by filtration under suction.
The novel radical ion salts (I) may furthermore be prepared by electrolysis of a solution which contains an N,N'-dicyanoquinonediimine of the formula (II) and a salt containing one of the above cations (Mm⊕) in one of the above solvents, at from room temperature to -30° C. The temperature depends on the solubility of the N,N'-dicyanoquinoneimine. Preferably, electrolysis is carried out at <0° C., in particular from -10° to -30° C., in order as far as possible to avoid any decomposition which may occur. In this case too, the radical ion salts are isolated in a conventional manner by filtration under suction. The yield of the radical ion salt (I) depends on the duration of electrolysis and on the solubility of (I) in the solvent used for the electrolysis, since isolation of the dissolved salt (I) from the electrolysis solution containing the conductive salt is very difficult.
The radical ion salts (I) according to the invention can also be prepared by reacting the lithium salt of an N,N'-dicyanoquinonediimine of the formula (II) with a salt containing one of the above cations (Mm⊕) in a solvent such as methanol, ethanol, propanol, water, acetonitrile or a mixture of these.
Microcrystalline films which consist of the novel radical ion salts can be produced in a conventional manner by immersing a metallic body in a solution of an N,N'-dicyanoquinoneimine in one of the above solvents, preferably at elevated temperatures.
The Examples which follow illustrate the invention. Percentages for the yields are based on the theoretical yield. The stated conductivities are determined for powder pellets or single crystals.
A solution of 156 mg (100 millimoles) of N,N'-dicyano-1,4-benzoquinonediimine is added dropwise to a filtered solution of 1.34 g (10.0 ml) of lithium iodide in acetonitrile, while stirring. Stirring is continued for 10 minutes, after which the product is filtered off under suction and washed with acetonitrile to give 98 mg (52%) of the corresponding radical ion salt in the form of a pale violet powder which decomposes above 234° C.
Analysis: C8 H6 I0.06 Li1.06 N4 O. Calculated: C 50.81, H 3.20, I 4.03, N 29.64%. Found: C 51.43, H 3.19, I 3.93, N 28.98%.
A solution of copper(I) iodide in acetonitrile is added to a solution of N,N'-dicyanoquinonediimine (II) in acetonitrile. During this procedure, a dark precipitate separates out and is filtered off under suction and washed with acetonitrile. The N,N'-dicyanoquinonediimines (II) used are characterized by the substituents in columns 2 to 5 of Table 1.
The radical anion salts obtained are of the general formula (Ia) ##STR8##
The meanings of k, l, n, x and y are given in columns 6 to 10 in Table 1. In the Table, the salts (Ia) are characterized by the decomposition point and elemental analysis.
TABLE 1
__________________________________________________________________________
Elemental analysis
Decomposi-
Yield
Conducti-
Ex- C H N Other
tion point
[% of
vity
ample
R.sup.1
R.sup.2
R.sup.3
R.sup.4
k l n x y [%]
[%] [%]
elements
[°C.]
therory]
σ[S
·
cm.sup.-1
__________________________________________________________________________
]
2 H H H H 1 1 1 0 0 44.20
1.63
25.04
Cu: 28.2
from 265
75
3 CH.sub.3
H H H 1 1 1 0 0 45.81
2.69
23.45
Cu: 25.2
from 205
60
4 CH.sub.3
CH.sub.3
H H 1.3
1 1 0 0 51.47
3.59
23.83 from 205
51
5 CH.sub.3
H CH.sub.3
H 2 1 1 0 0 55.91
3.61
26.07 from 229
87
6 OCH.sub.3
H OCH.sub.3
H 3 2 2 0 0 46.78
3.09
21.96 from 280
78
7 Cl H Cl H 1.63
1 1 0 0 36.44
0.67
21.25 >350 46 2.5
8 CH.sub.3
CH.sub.3
CH.sub.3
H 1.75
0.91
1 0.09
0 54.91
4.19
23.27
I: 2.81
from 173
83
9 --(CH═CH).sub.2 --
H H 1.10
0.4
2 1.6
0 28.26
0.92
11.21
I: 36.78
>350 54 1.3 ·
10.sup.-2
10 Cl H CH.sub.3
H 2 1 1 0 0 42.47
1.81
21.42 >350 98 0.4
11 --(CH═CH).sub.2 --
H H 5 4 4 0 0 55.23
3.82
21.40 >350 78
__________________________________________________________________________
The procedure described in Example 1 is followed, except that a solution of copper(I) bromide in tetrahydrofuran is used, and a solution of 2-chloro-5-methyl-N,N'-dicyano-1,4-benzoquinonediimine is added dropwise to this. The corresponding radical ion salt of the formula ##STR9## is obtained in a yield of 93%. Mp.>350° C.
C9 H5 N4 ClCu. Calculated: C 45.73, H 2.13, N 23.70%. Found: C 45.40, H 1.85, N 23.42%.
Conductivity: 0.4 S.cm-1 (powder).
N,N'-Dicyanoquinonediimines (II) are stirred with silver powder in acetonitrile at room temperature. Insoluble material is filtered off under suction. The N,N'-dicyanoquinonediimines (II) used are characterized by R1 to R4 in columns 2 to 5 of Table 2.
The radical ion salts obtained are of the general formula (Ib) ##STR10##
The meanings of k, n and y are given in columns 6 to 9.
In Table 2, the salts (Ib) are characterized by the decomposition point, elemental analysis and the electrical conductivity.
TABLE 2
__________________________________________________________________________
Elemental analysis
Decomposi-
C H N tion point
Conductivity
Example
R.sup.1
R.sup.2
R.sup.3
R.sup.4
k n [%]
[%] [%]
[°C.]
σ[Scm.sup.-1 ]
__________________________________________________________________________
13 H H H H 1 1 36.41
1.32
20.86
>350 1.7 19 10.sup.-2
14 Cl
H Cl
H 1.1
1 30.05
0.36
16.93
>350 19.8
15 H H Cl
H 1.62
1 32.95
0.69
19.22
>350 8 · 10.sup.-2
__________________________________________________________________________
Electrolysis is carried out in a cell which holds 60 ml of liquid and is divided into 3 compartments by two G4 glass frits. Each compartment can be filled or emptied under protective gas, independently of one another.
The electrodes are present in the outer compartments. Dividing the cell into three parts prevents byproducts formed at the anode from penetrating into the cathode space.
Two platinum sheets measuring 20×10×1 mm are used as the electrodes. The electrodes and the cell are cleaned with a mixture of 35% strength hydrogen peroxide and concentrated sulfuric acid each time before being used. They are then washed with water, after which the cell is steeped in distilled water for 1 day in order to remove final traces of acid. The cell is then dried at 120° C.
Current is supplied by a constant current source which can be regulated between 0 and 250 μA.
By adjusting the cell temperature in a heatable bath, electrolysis can be effected at defined temperatures.
To carry out the electrolysis, a solution of 92 mg (500 μmol) of N,N'-dicyano-2,5-dimethyl-1,4-benzoquinonediimine and 170 mg (=1.00 millimole) of silver nitrate in 60 ml of acetonitrile is introduced into all three compartments of the cell, and electrolysis is effected at room temperature, using a current of 3 μA. Thin acicular crystals up to 3 cm long grow at the cathode. After 80 hours, 12 mg (10%) of silver salt are isolated in the form of deep black needles of melting point 205° C. (decomposition).
Analysis (476.3): C20 H16 AgN8. Calculated: C 50.43, H 3.39, N 23.53%. Found: C 50.42, H 3.29, N 22.91%.
Electrolysis of the solution is not taken to completion, in order to avoid excessive reduction.
A solution of 68 mg (=302 μmol) of N,N'-dicyano-2,5-dichloro-1,4-benzoquinonediimine and 368 mg (2.27 millimoles) of tetramethylammonium tetrafluoborate in acetonitrile is subjected to electrolysis at -25° C., using a current of 50 μA. After 40 hours, the black needles up to 2 mm long which are deposited at the cathode and exhibit metallic gloss are collected, and washed with diethyl ether. 20 mg (25%) of the radical salt of melting point 220° C. (decomposition) are obtained.
Analysis (476.3): C22 H16 AgN9. Calculated: C 45.82, H 3.00, N 24.05%. Found: C 46.37, H 3.10, N 23.95%.
The N,N'-dicyanoquinonediimines (II) characterized in Table 3 by R1, R2, R3 and R4 are subjected to electrolysis together with salts containing cations Mm⊕, in acetonitrile, using procedures similar to those described in Examples 15 and 16. Electrolysis is carried out at between room temperature (25° C.) and -20° to -25° C., depending on the solubility of the N,N'-dicyanoquinonediimines (II) used. The yield of (I) is dependent on the duration of electrolysis and on the solubility of the resulting compound (I) in acetonitrile. Isolation of the dissolved compound (I) from the acetonitrile solution formed during electrolysis and containing the conductive salt is very difficult.
Radical ion salts of the general formula (Ic) are obtained. ##STR11##
The meanings of k, Mm⊕ and n are given in Table 3 (columns 6 to 8).
The salts (Ic) obtained are characterized in columns 9 to 12 by their decomposition points and elemental analysis, and in some cases by their conductivities.
TABLE 3
__________________________________________________________________________
Elemental analysis
Decomposi-
Yield
Conducti-
Ex- C H N tion point
[% of
vity
ample
R.sup.1
R.sup.2
R.sup.3
R.sup.4
H.sup.m ⊕.sup.1
k n [%]
[%]
[%] [°C.]
theory]
δ[S ·
cm.sup.-1 ]
__________________________________________________________________________
18 H H H H Ag.sup.⊕
1 1 36.41
1.38
21.04
from 270
8
19 CH.sub.3
CH.sub.3
H H Ag.sup.⊕
1 1 41.24
2.61
19.29
from 205
8
20 CH.sub.3
H CH.sub.3
H Ag.sup.⊕
2 1 50.42
3.29
22.91
205 10 18
21 CH.sub.3
H Cl H Ag.sup.⊕
2 1 41.41
1.88
21.41
from 207
38
22 Cl H Cl H Ag.sup.⊕
1.7
1 33.25
0.20
19.70
from 305
24
23 Br H Br H Ag.sup.⊕
3 2 25.03
1.06
14.35
> 350 15
24 Cl H Cl H THA.sup.⊕
2 1 46.37
3.10
23.95
from 220
25 2 · 10.sup.-2
25 Br H Br H THA.sup.⊕
3 2 35.82
2.89
17.43
from 205
6
26 Cl H Cl H NHQ.sup.⊕
1.7
1 54.13
2.30
20.68
from 217
45 0.1
27 Br H Br H NHQ.sup.⊕
5 4 45.01
2.23
15.36
198 19
28 Br H Br H NHQ.sup.⊕
3 2 42.67
2.02
16.09
from 218
43
29 Cl H Cl H Q.sup.⊕
1 1 57.16
2.81
20.11
from 126
25
30 H H H H NMP.sup.⊕
2 1 68.53
3.89
27.25
125 8
31 Cl H Cl H NHP.sup.⊕
1 1 60.67
3.09
19.83
149 26
32 Br H Br H NHP.sup.⊕
1 1 47.10
2.47
15.85
from 121
7
.sup.(1) TMA.sup.⊕ = tetramethylammonium, NMQ.sup.⊕ =
N--methylquinolinium, Q.sup.⊕ = quinolinium, NMP.sup.⊕ =
N--methylphenazinium
33 CH.sub.3
H Br H Ag.sup.⊕
2 1 35.85
1.68
18.94
>350 45
34 --(CH.sub.2).sub.4 --
H H Cu.sup.⊕
5 4 55.11
3.73
21.84
>350 58
35 Cl H Cl H Cu.sup.⊕
1 1 32.59
0.73
18.83
>350 22 0.08.sup.(1)
36 --(CH═CH).sub.2 --
Cl Cl
Ag.sup.⊕
1 1 36.89
1.02
14.21
>350 38 0.02.sup.(1)
37 OCH.sub.3
H OCH.sub.3
H Cu.sup.⊕
1 1 44.35
3.10
20.43
>350 22 0.7.sup.(1)
38 H H H H Cu.sup.⊕
1 1 43.24
1.85
25.59
>270 52 0.02.sup.(1)
39 CH.sub.3
H Cl H Cu.sup.⊕
2 1 41.81
1.95
21.67
>350 46 300.sup.(2)
0.4.sup.(1)
40 CH.sub.3
H Br H Cu.sup.⊕
2 1 37.88
1.80
19.72
>350 86 0.3.sup.(1)
__________________________________________________________________________
.sup.(1) measured on microcrystalline powder
.sup.(2) measured on the single crystal
Claims (10)
1. A radical ion salt of the formula: ##STR12## wherein R1, R2, R3 and R4 independently of one another are each hydrogen, methyl, ethyl, phenyl, methoxy, ethoxy, fluorine, chlorine or bromine; or R1 or R1 and R3 are each tert-butyl; or R1 and R2 or R3 and R4 or R1 and R2 and R3 and R4 together form a radical of the formula: ##STR13## wherein z is 0, 1, 2 or 3, and wherein the fused aromatic rings are substituted by chlorine, bromine, methyl or methoxy, Mm+ is a cation whose redox potential is less than or equal to that of silver and which is selected from the group consisting of m-valent alkali metals, copper, silver and tetra-C1 -C4 -alkyl ammonium, tetraphenyl-C1 -C3 -alkyl ammonium, phenyl-C1 -C3 -alkyl-tris-C1 -C4 -alkyl ammonium, C1 -C4 -alkylpyridinium, N-(phenyl-C1 -C3 -alkyl)-pyridinium, quinolinium, N-C1 -C4 -alkylquinolinium, N-(phenyl-C1 -C3 -alkyl)-quinolinium, isoquinolinium, N-C1 -C4 -alkylisoquinolium, N-(phenyl-C1 -C3 -alkyl)-isoquinolinium, phenazinium, N-C1 -C4 -alkylphenazinium or N-(phenyl-C1 -C3 -alkyl)-phenazinium; and wherein k is from 1 to 5, l is from 0.1 to 4, m is from 1 to 3, n is from 0.1 to 4, x is from 0 to 2 and y is from 0 to 6, or k, l, n, x and y are non-integral numbers wherein the number of negative charges on the radical (l-) plus the number of iodine anions (x) is equal to the number of metal cations multiplied by the number of positive charges per metal cation, thereby ensuring that the radical ion salt is neutral.
2. The radical ion salt as claimed in claim 1, wherein said substituted fused aromatic rings are mono- or di-substituted by chlorine, bromine, methyl or methoxy.
3. A radical ion salt of the formula: ##STR14## where R1 and R3 are each hydrogen, methyl, methoxy, chlorine or bromine; R2 is hydrogen or methyl and R4 is hydrogen; or R1 and R2 together are of the formula: ##STR15## and wherein Mm+ is a copper or silver ion or pyridinium, N-methylpyridinium, quinolinium, N-methylquinolinium, phenazinium or N-methylphenazinium, k is from 1 to 5, l is from 0.1 to 4, m is from 1 to 3, n is from 0.1 to 4, x is from 0 to 2, or k, l, n and x are non-integral numbers and, wherein the number of negative charges on the radical ion (l-) plus the number of iodine anions (x) is equal to the number of metal cations multiplied by the number of positive charges per metal cation, thereby ensuring that the radical ion salt is neutral.
4. The radical ion salt as claimed in claim 1, wherein Mm⊕ is a copper(I) or silver ion or tetramethylammonium, tetraethylbenzylammonium, tetrabenzylammonium, trimethylbenzylammonium, triethylammonium, quinolinium, pyridinium, N-methylpyridinium, N-ethylquinolinium, N-methylquinolinium, phenazinium or N-methylphenazinium.
5. The radical ion salt of the formula according to claim 1, wherein Mm⊕ is a copper(I) or silver ion or pyridinium, N-methylpyridinium, quinolinium, N-methylquinolinium, phenazinium or N-methylphenazinium.
6. The radical ion salt as claimed in claim 1, wherein R1, R2, R3 and R4 are each hydrogen, fluorine, chlorine, methyl or methoxy or R1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R2, R3 and R4 are each hydrogen, or R1 and R4 are each chlorine, methyl or methoxy and R2 and R3 are each hydrogen, or R1 and R2 are each chlorine, methyl, methoxy or phenyl and R3 and R4 are each hydrogen, or R1 and R3 are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R2 and R4 are each hydrogen, or R1, R2 and R3 are each methyl and R4 is hydrogen, or R1 is methyl, R3 is chlorine or bromine and R2 and R4 are each hydrogen, or R1 and R2 together form a radical of the formula: ##STR16## where z is 1 or 2, and the fused benzene ring is unsubstituted or monosubstituted or disubstituted by chlorine, methyl or methoxy, and R3 and R4 independently of one another are each hydrogen, chlorine or methyl.
7. The radical ion salt as claimed in claim 1, wherein R1, R2, R3 and R4 are each hydrogen, fluorine, chlorine, methyl or methoxy or R1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R2, R3 and R4 are each hydrogen, or R1 and R4 are each chlorine, methyl or methoxy and R2 and R3 are each hydrogen, or R1 and R2 are each chlorine, methyl, methoxy or phenyl and R3 and R4 are each hydrogen, or R1 and R3 are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R2 and R4 are each hydrogen, or R1, R2 and R3 are each methyl and R4 is hydrogen, or R1 is methyl, R3 is chlorine or bromine and R2 and R4 are each hydrogen, or R1 and R2 together form a radical of the formula ##STR17## where z is 1 or 2, and the fused benzene ring is unsubstitued or monosubstituted or disubstituted by chlorine, methyl or methoxy, and R3 and R4 independently of one another are each hydrogen, chlorine or methyl.
8. The radical ion salt as claimed in claim 1, wherein R1, R2, R3 and R4 are each hydrogen, fluorine, chlorine, methyl or methoxy, or R1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R2, R3 and R4 are each hydrogen, or R1 and R4 are each chlorine, methyl or methoxy and R2 and R3 are each hydrogen, or R1 and R2 are each chlorine, methyl, methoxy or phenyl and R3 and R4 are each hydrogen, or R1 and R3 are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R2 and R4 are each hydrogen, or R1, R2 and R3 are each methyl and R4 is hydrogen, or R1 is methyl, R3 is chlorine or bromine and R2 and R4 are each hydrogen, or R1 and R2 together form a radical of the formula ##STR18## where z is 1 or 2, and the fused benzene ring is unsubstituted or monosubstituted or disubstituted by chlorine, methyl or methoxy, and R3 and R4 independently of one another are each hydrogen, chlorine or methyl.
9. The radical ion salt as claimed in claim 4, wherein R1, R2, R3 and R4 are each hydrogen, fluorine, chlorine, methyl or methoxy, or R1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R2, R3 and R4 are each hydrogen, or R1 and R4 are each chlorine, methyl or methoxy and R2 and R3 are each hydrogen, or R1 and R2 are each chlorine, methyl, methoxy or phenyl and R3 and R4 are each hydrogen, or R1 and R3 are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R2 and R4 are each hydrogen, or R1, R2 and R3 are each methyl and R4 is hydrogen, or R1 is methyl, R3 is chlorine or bromine and R2 and R4 are each hydrogen, or R1 and R2 together form a radical of the formula ##STR19## where z is 1 or 2, and the fused benzene ring is unsubstituted or monosubstituted or disubstituted by chlorine, methyl or methoxy, and R3 and R4 independently of one another are each hydrogen, chlorine or methyl.
10. The radical ion salt as claimed in claim 5, wherein R1, R2, R3 and R4 are each hydrogen, fluorine, chlorine, methyl or methoxy, or R1 is chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenyl or tert-butyl and R2, R3 and R4 are each hydrogen, or R1 and R4 are each chlorine, methyl or methoxy and R2 and R3 are each hydrogen, or R1 and R2 are each chlorine, methyl, methoxy or phenyl and R3 and R4 are each hydrogen, or R1 and R3 are each chlorine, bromine, methyl, ethyl, methoxy, phenyl or tert-butyl and R2 and R4 are each hydrogen, or R1, R2 and R3 are each methyl and R4 is hydrogen, or R1 is methyl, R3 is chlorine or bromine and R2 and R4 are each hydrogen, or R1 and R2 together form a radical of the formula ##STR20## where z is 1 or 2, and the fused benzene ring is unsubstituted or monosubstituted or disubstituted by chlorine, methyl or methoxy, and R3 and R4 independently of one another are each hydrogen, chlorine or methyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3522232 | 1985-06-21 | ||
| DE19853522232 DE3522232A1 (en) | 1985-06-21 | 1985-06-21 | RADIKALION SALTS |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06876399 Continuation | 1986-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4885368A true US4885368A (en) | 1989-12-05 |
Family
ID=6273830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/125,823 Expired - Fee Related US4885368A (en) | 1985-06-21 | 1987-11-23 | Radical ion salts |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4885368A (en) |
| EP (1) | EP0206266B1 (en) |
| JP (1) | JPS61293962A (en) |
| DE (2) | DE3522232A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5216661A (en) * | 1991-07-22 | 1993-06-01 | The Johns Hopkins University | Electron density storage device using a stm |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3718365A1 (en) * | 1987-06-02 | 1988-12-22 | Basf Ag | N, N'-BISCYANO-P-BENZOQUINONE BISIMINE, THESE CHARGE TRANSFER COMPLEXES AND RADICALION SALTS CONTAINING THE BISCYANO-BENZOQUINONE BISIMINE |
| CA2223562A1 (en) | 1997-12-02 | 1999-06-02 | Hydro-Quebec | New electrode material derived from ionic polyquinoid compounds, and their uses, especially in electrochemical generators |
| DE10357044A1 (en) * | 2003-12-04 | 2005-07-14 | Novaled Gmbh | Process for doping organic semiconductors with quinonediimine derivatives |
| JP5043551B2 (en) * | 2007-08-01 | 2012-10-10 | 株式会社デンソー | Nonaqueous electrolyte secondary battery using high molecular weight polymer containing nitroxy radical group |
| JP5483523B2 (en) * | 2008-08-28 | 2014-05-07 | 公立大学法人大阪市立大学 | Electrode active material and secondary battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2762811A (en) * | 1955-05-26 | 1956-09-11 | Du Pont | Acyclic polynitrile-containing, unsaturated compounds and prepartion thereof |
| US2779780A (en) * | 1955-03-01 | 1957-01-29 | Du Pont | 1, 4-diamino-2, 3-dicyano-1, 4-bis (substituted mercapto) butadienes and their preparation |
| US3051736A (en) * | 1960-12-27 | 1962-08-28 | Union Carbide Corp | Cuprous complexes |
| US3644453A (en) * | 1969-12-11 | 1972-02-22 | Halcon International Inc | Cuprous halide and adiponitrile complexes |
| US3711527A (en) * | 1969-02-10 | 1973-01-16 | Bayer Ag | Process for the production of 3,4-unsaturated nitriles |
| DE3437814A1 (en) * | 1983-10-19 | 1985-05-02 | Basf Ag, 6700 Ludwigshafen | Charge transfer complexes |
| US4578220A (en) * | 1983-10-19 | 1986-03-25 | Basf Aktiengesellschaft | Charge transfer complexes of tetrathio/seleno-fulvalene derivatives and biscyanimine derivatives; biscyanimine derivatives and method for producing same |
-
1985
- 1985-06-21 DE DE19853522232 patent/DE3522232A1/en not_active Withdrawn
-
1986
- 1986-06-13 JP JP61136370A patent/JPS61293962A/en active Pending
- 1986-06-19 DE DE8686108389T patent/DE3665171D1/en not_active Expired
- 1986-06-19 EP EP86108389A patent/EP0206266B1/en not_active Expired
-
1987
- 1987-11-23 US US07/125,823 patent/US4885368A/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2779780A (en) * | 1955-03-01 | 1957-01-29 | Du Pont | 1, 4-diamino-2, 3-dicyano-1, 4-bis (substituted mercapto) butadienes and their preparation |
| US2762811A (en) * | 1955-05-26 | 1956-09-11 | Du Pont | Acyclic polynitrile-containing, unsaturated compounds and prepartion thereof |
| US3051736A (en) * | 1960-12-27 | 1962-08-28 | Union Carbide Corp | Cuprous complexes |
| US3711527A (en) * | 1969-02-10 | 1973-01-16 | Bayer Ag | Process for the production of 3,4-unsaturated nitriles |
| US3644453A (en) * | 1969-12-11 | 1972-02-22 | Halcon International Inc | Cuprous halide and adiponitrile complexes |
| DE3437814A1 (en) * | 1983-10-19 | 1985-05-02 | Basf Ag, 6700 Ludwigshafen | Charge transfer complexes |
| US4578220A (en) * | 1983-10-19 | 1986-03-25 | Basf Aktiengesellschaft | Charge transfer complexes of tetrathio/seleno-fulvalene derivatives and biscyanimine derivatives; biscyanimine derivatives and method for producing same |
Non-Patent Citations (3)
| Title |
|---|
| Chemical Abstracts vol. 101:38122f (1984). * |
| Chemical Abstracts vol. 103:104661c (1985). * |
| Chemical Abstracts vol. 103:141935r (1985). * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5216661A (en) * | 1991-07-22 | 1993-06-01 | The Johns Hopkins University | Electron density storage device using a stm |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3522232A1 (en) | 1987-01-02 |
| DE3665171D1 (en) | 1989-09-28 |
| EP0206266A3 (en) | 1987-10-21 |
| EP0206266B1 (en) | 1989-08-23 |
| JPS61293962A (en) | 1986-12-24 |
| EP0206266A2 (en) | 1986-12-30 |
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